Role of Radical Elimination Reactions with Concerted Fragmentation in the Chain Decomposition of Alkyl Nitrates

2017 ◽  
Vol 58 (6) ◽  
pp. 679-687 ◽  
Author(s):  
E. T. Denisov ◽  
A. F. Shestakov
2019 ◽  
Vol 123 (13) ◽  
pp. 2621-2633 ◽  
Author(s):  
Blanton R. Gillespie ◽  
Chaitanya A. Patel ◽  
Mallory M. Rothrock ◽  
George L. Heard ◽  
D. W. Setser ◽  
...  

2013 ◽  
Vol 13 (1) ◽  
pp. 1979-2034 ◽  
Author(s):  
J. L. Fry ◽  
D. C. Draper ◽  
K. J. Zarzana ◽  
P. Campuzano-Jost ◽  
D. A. Day ◽  
...  

Abstract. At the Rocky Mountain Biogenic Aerosol Study (BEACHON-RoMBAS) field campaign in the Colorado front range, July–August 2011, measurements of gas- and aerosol-phase organic nitrates enabled a study of the role of NOx (NOx = NO + NO2) in oxidation of forest-emitted VOCs and subsequent aerosol formation. Substantial formation of peroxy- and alkyl-nitrates is observed every morning, with an apparent 2.9% yield of alkyl nitrates from daytime RO2 + NO reactions. Aerosol-phase organic nitrates, however, peak in concentration during the night, with concentrations up to 140 ppt as measured by both optical spectroscopic and mass spectrometric instruments. The diurnal cycle in aerosol fraction of organic nitrates shows an equilibrium-like response to the diurnal temperature cycle, suggesting some reversible absorptive partitioning, but the full dynamic range cannot be reproduced by thermodynamic repartitioning alone. Nighttime aerosol organic nitrate is observed to be positively correlated with [NO2] × [O3] but not with [O3]. These observations support the role of nighttime NO3-initiated oxidation of monoterpenes as a significant source of nighttime aerosol. Nighttime production of organic nitrates exceeds daytime photochemical production at this site, which we postulate to be representative of the Colorado front range forests.


2009 ◽  
Vol 48 (8) ◽  
pp. 3667-3678 ◽  
Author(s):  
Oleg A. Filippov ◽  
Victoria N. Tsupreva ◽  
Lyudmila M. Golubinskaya ◽  
Antonina I. Krylova ◽  
Vladimir I. Bregadze ◽  
...  

2014 ◽  
Vol 14 (22) ◽  
pp. 12441-12454 ◽  
Author(s):  
L. Lee ◽  
P. J. Wooldridge ◽  
J. B. Gilman ◽  
C. Warneke ◽  
J. de Gouw ◽  
...  

Abstract. Nitrogen dioxide (NO2) and total alkyl nitrates (ΣANs) were measured using thermal dissociation laser-induced fluorescence during the 2012 Uintah Basin Winter Ozone Study (UBWOS) in Utah, USA. The observed NO2 concentration was highest before sunrise and lowest in the late afternoon, suggestive of a persistent local source of NO2 coupled with turbulent mixing out of the boundary layer. In contrast, ΣANs co-varied with solar radiation with a noontime maximum, indicating that local photochemical production combined with rapid mixing and/or deposition was the dominant factor in determining the ΣAN concentrations. We calculate that ΣANs were a large fraction (~60%) of the HOx free radical chain termination and show that the temperature dependence of the alkyl nitrate yields enhances the role of ΣANs in local chemistry during winter by comparison to what would occur in the warmer temperatures of summer.


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